Fungi and bacteria resistant polyvinyl halide compositions



Patented Sept. 21, 1954 FUNGI AND BACTERIA RESISTANT POLY- VINYL HALIDECOMPOSITIONS Joseph R. Darby, Richmond Heights, and Elmer E. Cowell, St.Louis, Mo.,assignors to Monsanto Chemical Company, St. Louis, Mo., acorporation of Delaware No Drawing. Application March 2, 1951,

Serial No. 213,666

12 Claims. 1

This invention relates to improved resinous compositions containingpolymerized vinyl halide. More particularly, this invention relates toan improved process for the preparation of plasticized resinouscompositions having improved resistance to deterioration due to attackby such micro-organisms as fungi and bacteria, and containingpolymerized vinyl halide, copolymers containing combined vinyl halide,or combinations thereof containing combinedvinyl halide, collectivelyand broadly referred to herein as polyvinyl halide compositions.

Polyvinyl halide compositions have found many useful applicationsbecause of their wide range of elastomeric and mechanical propertiescoupled with their extreme resistance to oxidation, organic solvents,acids and alkalies. Typical of such applications are calendered filmsand sheeting for Wearing apparel, shower curtains and seat and cushioncoverings. In such applications, polyvinyl halide compositions havefound utility as a free or unsupported film but more frequentlypolyvinyl halide compositions have been used to coat such textiles ascotton, wool, silk, rayon,

and nylon thereby obtaining a composition or fabric for use in the abovementioned applications which combines the desirable properties of thetextile and the desirable properties of the polyvinyl halidecomposition. halide compositions frequently contain plasticizers orstabilizers which have their origin in animal or vegetable sources, orthe base material of coated compositions frequently contains materialswhich have their origin in animal or vegetable sources which therebyrender the resultant Such polyvinyl composition quitesusceptible todeteriorating attack by such micro-organisms as fungi and bacteria. Suchdeterioration of polyvinyl halide compositionsor polyvinyl halide coatedcompositions seriously hinders full scale utility of the compositionsparticularly in those areas and those applications which are conduciveto such an attack.

Copper S-quinolinolate is a Well known fungicideand bactericide, andrepeated attempts have been made to incorporate this material intopolyvinyl halide compositions in order to render such compositionsresistant to attacks by fungi and bacteria. It has been found, however,that copper 8-quinolinolate is exceedingly incompatible with polyvinylhalide compositions. According to th methods as heretofore practiced, ifeven minor amounts, of the order of 0.2% by weight of total composition,are incorporated into a plasticized polyvinyl halide composition, withinseveral hours after preparation of the composition the copperS-quinolinolate begins to crystallize or bloom on the surface of thecomposition indicating incompatibility and rendering the compositionunfit for use.

A more recent development in the field of fungi and bacteria resistantplasticized polyvinyl halide compositions has been the discovery of theuse of N-alkyl arylsulfonamides as a compatibilizing agent for copper8-quinolinolate in such compositions. According to, this procedure, acompatible plasticized polyvinyl halide composition containing copper8-quinolinolate is prepared by incorporating therein an N-alkyl arylsulfonamide. While this procedure has been most successful in manyapplications, a surprising phenomenon has been found to exist. It hasbeen observed that if such a composition is utilized in an applicationwhich prevents the composition from being exposed to ultra-violet light,after a period of time copper S-quinolinolate begins to exude orcrystallize upon the surface of the composition, thereby indicatingincompatibility. Thus, if such compositions are utilized as theinsulation or coat ing for wires which will be constantly keptunderground or sealed in the walls of buildings, or if such compositionsare used as the inside coating for tent fabrics in which applicationsthe compositions will never be subject to the effects of ultra-violetlight, after a short period. of time copper 8-quinolinolate can beobserved crystallizing upon the surface of such compositions.

It is an object of this invention, therefore, to provide an improvedprocess for the preparation of plasticized polyvinyl halide compositionshaving incorporated therein copper 8-quinolinolate so as to render themresistant to attack by fungi and bacteria, which compositions willremain compatible and homogeneous with no evidence of crystallization orblooming of the copper S-quinolinolate under any conditions ofapplication or use. Further objects will become apparent from thedescription of the novel process of this invention.

According to the process heretofore used, fungi and bacteria resistantplasticized polyvinyl halide compositions have been prepared by merelymixing the resin, the plasticizer, copper 8-quinolinelate and thecompatibilizing agent as one mixture under the influence of heat or in asuitable solvent until a homogeneous mass was obtained. Compositions soprepared develop incompatibility in the absence of the effects ofultra-violet light as previously indicated. It has now been discoveredthat if the plasticizer, copper S-quinolinolate and the compatibilizingagent are first mixed in the presence of heat to form a substantiallyhomogeneous composition, and the homogeneous composition thus obtainedthen incorporated into the particular polyvinyl halide resin desired, afungi and bacteria resistant plasticized polyvinyl halide compositionresults which will remain compatible even in the absence of ultra-violetradiation. According to the novel process of this invention, therefore,compatible fungi and bacteria resistant plasticized: polyvinyl halidecompositions are prepared, which compositions will retain theircompatibility and homogeneity even in those applications wherein theyare not subjected to the effect of ultra-violet radiation, byincorporating into the vinyl halide polymer utilized in the composition,a substantially homogeneous composition obtained by heating a mixturecomprising a plasticizer for said resin, a minor amount of copperS-quinolinolate and a compound selected from the group consisting ofN-alkyl benzenesulfonamides and N-alkyl toluenesulfonarnides wherein thealkyl group contains at least 1 and not more than 8 carbon atoms.

The following examples are illustrative, but not limitative of the novelprocess of this invention. All parts are parts by weight unlessotherwise noted.

Example I 100 parts of polyvinyl chloride, 2.5 parts of tricresylphosphate, 2.5 parts of butyl acetyl ric inoleate and 1 part of copper8-quinolinolate are mixed together at room temperature in a suitablecontainer. The mixture is then placed on a differential speed roll milland further mixed and fluxed for 5 minutes at 160 C. At the end of thistime, a homogeneous composition is formed which is sheeted off the rollmill. 0.040 inch thicl; sheets of the composition so prepared are thenmolded at a temperature of 160 C. under a pressure of 2000 pounds persquare inch. Shortly after removal from the mold, crystals of copper8-quinolinolate can be observed on the surface of the compositionthereby indicating incompatibility of the copper 8-quinolinolate.

Example II The procedure set forth in Example I is repeated utilizing inaddition to the ingredients set forth therein, 5 parts of N-methylbenzensulfonamide. The molded specimen when removed from the mold isfree of any signsof blooming or crystallization, thereby indicating acompatible composition. In order to further test the compatibility ofthe composition so prepared,,specimens molded as above described areallowed to stand on a table in ordinary daylight. Similar specimens areplaced in a closed cabinet from which all daylight is excluded. Afterabout 30 days, the specimens which are exposed to daylight are free ofany signs of blooming or crystallization, indicating a compatiblecomposition, whereas the compositions which are kept in the cabinet fromwhich daylight is excluded, exhibit crystallization or blooming ofcopper 8-quinolinolate on the surface of the composition, therebyindicating that the copper 8-quinolinolate has become incompatible withthe resinous composition.

Example III 2.5 parts of tricresyl phosphate, 2.5 parts of butyl acetylricinoleate, 5 parts of N-methyl benzenesulfonamide and 1 part of copper8-quinolinolate are placed in a suitable container, heated to atemperature of about 160 C. and stirred until a homogeneous mixtureresults. The homogeneous liquid composition thus obtained is then mixedwith 100 parts of polyvinyl chloride and placed on a differential speedroll mill and further mixed and fluxed for 5 minutes at 160 C. Theresulting composition is then molded as described in Example I. Themolded specimens are free of any signs of blooming or crystallization,thereby indicating a compatible composition. Specimens of the moldedcomposition thus prepared are allowed to stand in the presence ofdaylight while similar specimens are placed in a cabinet from whichdaylight is excluded. After days the specimens which have been allowedto stand in the presence of daylight and those specimens which have beenallowed to stand in the absence of daylight are free from any signs ofblooming or crystallization, thereby indicating completely compatiblecompositions. It is evident, therefore, that the preheating treatmentapplied to the plasticizer mixture prior to incorporation into thepolyvinyl chloride resin permitted the preparation of a compatibleplasticized polyvinyl halide composition having incorporated thereincopper S-quinolinolate, which composition retained its compatibilityeven on prolonged standing in the absence of ultra-violet light.

Example IV A composition comprising parts of polyvinyl chloride, 25parts of tricresyl phosphate, 25 parts of butyl acetyl ricinoleate, and0.2 part of copper B-quinolinolate is processed in the manner describedin Example I. The molded specimen exhibits blooming and a crystalformation on the surface thereby indicating that copper S-quinolinolatewas incompatible in this composition.

Example V The procedure set forth in Example IV is repeated utilizing inaddition to the ingredients set forth therein, 5 parts ofN-fi-methylheptyl benzenesulfonamide. The molded specimen when removedfrom the mold is free of any signs of blooming or crystallization,thereby indicating a compatible composition. Specimens of the moldedcomposition are allowed to stand on a table in ordinary daylight whilesimilar specimens are placed in a closed cabinet from which all daylightis excluded. After about 30 days, the specimens which are exposed todaylight are free of any signs of blooming or crystallization whereasthe specimens which are kept in the cabinet from which daylight isexcluded exhibit crystallization or blooming of copper 8-quinolinolateon the surface of the composition.

Example VI 25 parts of tricresyl phosphate, 25 parts of butyl acetylricinoleate, 5 parts of N-G-methylheptyl benzenesulfonamide and 0.2 partof copper, B-quinolinolate are placed in a suitable container, heated toa temperature of about C. and

stirred until a homogeneous mixture results. The. homogeneous liquidcomposition thus obtainedis then mixed with 100 parts of polyvinylchloride and placed on a diiferential speed roll mill and further mixedand fluxed for about 5 minutes at 160 C. The resulting homogeneouscomposition is then molded as described in Example I. The moldedspecimens are free of any signsof blooming or crystallization. Specimensof the molded composition thus prepared are allowed to stand in thepresence of daylight while similar specimens are placed in a cabinetfrom which daylight is excluded. After 90 days the specimens which havebeen allowed to stand in the presence of daylight and those specimenswhich have been allowed to stand in the absence of daylight are freefrom any signs of blooming or crystallization, thereby indicatingcompletely compatible compositions. Earample VII In accordance with theprocedure described in Example VI, a composition was prepared containing100 parts of polyvinyl chloride, 25 parts of tricresyl phosphate, 25parts of butyl acetyl ricinoleate, parts of N-ethyl-p-toluenesulfonamideand 1 part of copper 8-quinolinolate. The composition thus preparedevidences no signs of incompatibility even when retained for prolongedperiods of time in the absence of daylight.

A cotton duck fabric is coated with the composition described in ExampleVII by the calendering method which consists in simultaneously passingthe fabric and the polyvinyl chloride composition through a conventionalfour-roll calender. The coated cotton duck fabric in addition topossessing the desirable characteristics of the fabric and the polyvinylchloride coating, is extremely resistant to attack by fungi and bacteriaby virtue of the composition having incorporated therein copperS-quinolinolate.

Example VIII A composition comprising 100 parts of polyvinyl chloride,25 parts of dioctyl phthalate and 1.5 parts of copper 8-quinolinolate,is prepared by the manner described in Example I. The molded specimenexhibits blooming and crystallization on the surface indicating theincompatibility of copper 8-quinolinolate in this composition.

Example IX The procedure set forth in Example VIII is repeated utilizingin addition to the ingredients set forth therein, 10 parts ofN-butyl-o-toluenesulfonamide. Molded specimens of the composition thusprepared are allowed to stand in the presence of daylight while similarspecimens of the molded compositions are allowed to stand in the absenceof daylight. Those compositions which are subjected to daylight orultra-violet light after a period of time show no signs ofincompatibility, while those compositions which are allowed to stand inthe absence of daylight, after a period of time begin to showincompatibility.

Example X 25 parts of dioctyl phthalate, 10 parts of N-butyl-o-toluenesulfonamide and 1.5 parts of copper S-quinolinolate areplaced in a suitable container, heated to a temperature of 160 C. andstirred until a homogeneous mixture results. The homogeneous liquidcomposition thus obtained is then mixed with 100 parts of polyvinylchloride and placed on a differential speed roll mill and further mixedand fluxed for 5 minutes at 160 C. The resulting homogeneous compositionis then molded as described in the preceding examples. Specimens of themolded composition are allowed to stand in the presence of daylightwhile similar specimens are allowed to stand in the absence of daylight.After prolonged standing under such conditions, neither specimen showsany signs of incompatibility.

Example XI 6 place of the 25 parts of dioctyl phthalate. The moldedspecimens thus obtained are: compatible and retain their compatibilityeven after prolonged standing in ultra-violet light.

Example XII The procedure set forth in Example X is repeated utilizingthe following ingredients:

parts of polyvinyl chloride 12.5 parts of dioctyl phthalate 12.5 partsof butyl acetyl ricinoleate 5 parts of copper S-quinolinolate 30 partsof N-2-ethylhexyl-p-toluenesulfonamide The procedure set forth inExample X is repeated utilizing the following ingredients:

100 parts of polyvinyl chloride 12.5 parts of dioctyl phthalate 12.5parts of butyl acetyl ricinoleate 2 parts of copper 8-quinolinolate 50parts of N-hexyl benzenesulfonamide The resulting composition iscompletely compatible even after prolonged standing in the absence ofultra-violet light. When a composition utilizing the above describedingredients is prepared in accordance with Example II, molded specimensthereof which are allowed to stand in the presence of ultra-violet lightshow no signs of incompatibility after prolonged standing, whereassamples which are allowed to stand in the absence of ultra-violet lightshow incompatibility after long standing.

Example XIV The procedure set forth in Example X is repeated utilizingthe following ingredients:

100 parts of polyvinyl chloride 12.5 parts of dioctyl phthalate 12.5parts of butyl acetyl ricinoleate 2 parts of copper 8-quinolinolate 30parts of N -isopropyl benzenesulfonamide The resulting composition iscompletely compatible even after prolonged standing in the absence ofultra-violet light. When a composition utilizing the above describedingredients :is prepared in accordance with Example II, molded specimensthereof which are allowed to stand in the presence of ultra-violet lightshow no signs of incompatibility after prolonged standing, whereassamples which are allowed to stand in the. absence of ultra-violet lightshow incompatibility after long standing.

Example XV The procedure set forth in Example X is repeated utilizingthe following ingredients:

100 parts of polyvinyl chloride 12.5 parts of dioctyl phthalate 12.5parts of butyl acetyl ricinoleate 2 parts of copper 8-quinolinolate 30parts of N -isopropyl-p-toluenesulfonamide The procedures set forth inExamples VIII, IX and X are repeated utilizing in place of the polyvinylchloride a polymerized vinyl resin containing90 parts of combined vinylchloride and parts of combined vinyl acetate. The properties of thecompositions thus prepared are similar to those obtained in ExamplesVIII, IX and X.

The procedures set forth in Examples VIII, IX and X are repeatedutilizing in place of the polyvinyl chloride a polymerized vinyl resincontaining 96 parts of combined vinyl chloride and 10 parts of diethylmaleate. The properties of the compositions thus prepared are similar tothose obtained in Examples VIII, IX and X.

Examples I, IV, VIII and XV (in part) as hereinbefore set forth veryclearly indicate the extreme incompatability of copper S-quinolinolatein polyvinyl halide compositions when such compositions are preparedaccording to the methods heretofore practiced. Examples II, V, IX, XII(in part), XIII (in part), XIV (in part) and XV (in part) illustrate thephenomenon of the compatibility of certain plasticized polyvinyl halidecompositions containing copper 3-quinolinolate in the presence ofultra-violet light and the unusual incompatibility of such compositionsin the absence of ultra-violet light when such compositions are preparedin accordance with recently developed processes. Examples III, VI, VII,X, XI, XII (in part), XIII (in part), XIV (in part) and XV (in part) areindicative of the outstanding compatability of copper 8-quinolinolate inplasticized polyvinyl halide compositions obtained when prepared inaccordance with the rocess of this invention whereby compositions areobtained which remain fully compatible even when retained for longperiods of time in the absence of ultra-violet light.

Samples of the polyvinyl chloride coated fabric prepared in Example VIIand unsupported polyvinyl chloride films prepared from the composi--tions set forth in Examples VI and X are inoculated with each of thefollowing organisms:

Chaetomz'um globosum, Metarrhizium sp., Aspergz'llus niger andPenicillium sp. and then incubated for 36 hours.

A further unsupported polyvinyl chloride film was prepared containing100 parts of polyvinyl chloride, parts of tricresyl phosphate and 25parts of butyl acetyl ricinoleate. When this composition was inoculatedwith the above mentioned organisms, a severe growth of the organism tookplace on the sample, indicating the outstanding '8 fungi and bacteriaresistant characteristics of the novel compositions of this invention.

7 While various specific embodiments of the novel process ofthis'invention have been particularly illustrated in the precedingexamples, it will be obvious to those skilled in the art thatsubstantial variation from the conditions set forth in these examples:is possible without departing from the scope of this invention. Forexample, in order to obtain fungi or bacteria resistant polyvinyl halidecompositions, it is preferable that such compositions contain from about0.1 to about 2.5 parts by weight of copper 8-quinolinolate'per parts ofpolymerized vinyl halide resin. At times, under severe conditions, it isdesirable to increase the copper S-quinolinolate content to about 5parts by weight per 100 parts of resin or even to 10 parts by weight per100 parts 'of resin.

The compositions prepared by the novel process of this invention maycontain any plasticizer for the polymerized vinyl halide resin utilizedin the composition, and the quantity of the plasticizer utilized may bevaried over a substantial range. Particularly advantageous compositionsare those which contain from about 5 parts to about parts by weight ofthe plasticizer per 100 parts of the polymerized vinyl halide resin.Typical of the various plasticizers which may be utilized in thecompositions prepared by the process of this invention are the arylalkane sulfonates; the various esters of phthalic acid such as dibutylphthalate, dioctyl phthalate, dinonyl phthalate, and alkyl benzylphthalates; the various esters of orthophosphorio acid such as the alkyldiaryl phosphates, tricresyl phosphate, trioctyl phosphate, etc.; estersof aliphatic dicarboxylic acids such as dibutyl sebacate, dioctyladipate, etc.; alkyl phthalyl alkyl glycolates such as butyl phthalylbutyl glycolate, etc. and resinous plasticizers such as the condensationproducts of polycarboxylic acids and polyhydric alcohols.

In addition to the usual plasticizers for polyvinyl halide resins, thecompositions prepared according to the process of this invention mayalso have incorporated therein various pigments, fillers, stabilizers,both heat and light, etc.

The N-alkyl arylsulfonamides which may be utilized in the compositionsprepared by the novel process of this invention are represented by thefollowing formula wherein R1 is a phenyl or cresyl radical and R2 is analkyl radical containing at least 1 and not more than 8 carbon atoms.Typical of the N- alkyl arylsulfonamides which can be so utilized arethe following:

N-methyl benzenesulfonamide N-ethyl benzenesulfonamide N-isopropylbenzenesulfonamide N-butyl benzenesulfonamide N-isobutylbenzenesulfonamide N-tert-butyl benzenesulfonamide N-hexylbenzenesulfonamide N-capryl benzenesulfonamide N-G-methylheptylbenzenesulfonamide N-Z-ethylhexyl benzenesulfonamideN-methyl-o-toluenesulfonamide N-ethyl-p-toluenesulfonamide N-isopropylm-toluenesulfonamide N-butyl-o-toluenesulfonamide 9N-tert-butyl-p-toluenesulfonamide N-iso-butyl-ptoluenesulfonamideN-hexyl-o-toluenesulfonamide N-capryl-p-toluenesulfonamideN-G-methylheptyl-p-toluenesulfonamideN-Z-ethylhexyl-p-toluenesulfonamide The quantity of the N-alkylarylsulfonamide utilized in the composition prepared by this inventionmay be varied over a substantial range. Particularly advantageouscompositions are those containing from about 1 to about 50 parts byweight, and preferably from about 1 to about 10 parts by Weight, of theN-alkyl arylsulfonamide per 100 parts of the polyvinyl halide resin.

As indicated by the examples, copolymers of a vinyl halide and otherunsaturated materials copolymerizable therewith may be utilized in thenovel process of this invention. For example, copolymers of vinylchloride with such materials as vinylidene chloride, vinyl esters ofcarboxylic acids, for example, vinyl acetate, vinyl propionate, vinylbutyrate, vinyl benzoate; esters of unsaturated acids, for example,alkyl acrylates, such as methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate, allyl acrylate and the corresponding esters ofmethacrylic acid; vinyl aromatic compounds, for example, styrene,ortho-chloro-styrene, para-chlorostyrene, 2,5-dichlorostyrene,2,4-dichlorostyrene, para-ethyl styrene, divinyl benzene, vinylnaphthanate, alpha-methyl styrene, dienes, such as butadiene,chloroprene; amides, such as acrylic acid amide, acrylic acid anilide;nitriles, such as acrylic acid nitrile; esters of alpha,beta-unsaturated carboxylic acids, for example, the methyl, ethyl,propyl, butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl, and phenylesters of maleic, crotom'c, itaconic, fumaric acids and the like. Theclass of copolymers in which a predominant portion i. e., more than 50%by weight, of the copolymer is made from vinyl chloride, represents apreferred class of polymers to be utilized in this invention.

base material and the polyvinyl chloride coatings, are thereby renderedextremely resistant to deterioration due to attack by fungi andbacteria. As indicatedin the examples, according to the novel process ofthis invention compatible plasticized polyvinyl halide compositions areprepared by first preparing a substantially ho mogeneous mixture of theplasticizer, N-alkyl arylsulfonamide and copper S-quinolinolate whichare to be utilized in the resinous composition and then incorporatingthis homogeneous mixture into the particular polyvinyl halide resin. Thepreparation of this homogeneous mixture of plasticizer, copperfi-quinolinolate and compatibilizing agent is accomplished by merelymixing the ingredients with heating until a substantially homogeneouscomposition results. The temperature during this heating period may bevaried over a substantial range and any elevated temperature which willpermit the preparation of the homogeneous mixture without anydecomposition of the mixture may be utilized. Temperatures in excess ofabout 100 C. are applicable although temperatures in the range of fromabout 140 C. to about 200 C. are particularly advantageous. Lowertemperatures may be utilized but longer periods of time may be requiredin such cases to effect substantially cornplete homogeneity. Similarly,temperatures higher than 200 C. may be utilized if desired.

By a substantially homogeneous mixture of the plasticizer, copperB-quinolinolate and compatibilizing agent is meant either asubstantially complete solution or a dispersion of the coppers-quinolinolate in the plasticizer and compatibilizing agent whichdispersion is macroscopically and substantially homogeneous althoughmicroscopically it may be of a heterogeneous nature.

A particularly preferred embodiment of this invention comprises the useof a polymer prepared by copolymerizing vinyl chloride and an ester ofan alpha, beta-unsaturated dicarboxylic acid, such as diethyl maleate,in which 5 to 20 parts by weight of diethyl maleate are utilized forevery 95 to 80 parts by weight of vinyl chloride. Among the preferredesters of alpha, betaunsaturated dicarboxylic acids are the alkyl estersin which the alkyl group contains from 1 to 8 carbon atoms.

In addition to the above described vinyl chloride-containing polymers,similar polymers wherein the vinyl chloride is replaced, either in wholeor in part, by other vinyl halides may be utilized. Typical of suchother vinyl halides are vinyl bromide, vinyl fluoride, etc.

The compositions prepared according to the novel process of thisinvention may be effectively utilized to produce free or unsupportedpolyvinyl halide films and. sheeting which will be resistant to thedeteriorating effects of fungi and bacteria. These compatiblecompositions may also be applied as a coating to various textiles, suchas, cotton, wool, rayon, silk, and nylon, and natural, synthetic, andartificial leathers. These compositions may be so applied by any of thewell known methods used to apply polyvinyl chloride coatings, such asthe conventional calender-ing, solvent coating, or dip coating methods.Such coated compositions, wherein the novel compositions of thisinvention are utilized, in addition to possessing the desirablecharacteristics of the In preparing this substantially homogeneousmixture of the plasticizer, copper 8-quinolinolate and compatibilizingagent, it is to be understood that all of the plasticizer and compatibilizing agent which is to be ultimately utilized in the finishedplasticized polyvinyl halide composition need not be utilized inpreparing the initially substantially homogeneous mixture unless such isso desired. Thus, for example, a substantially homogeneous mixture ofcopper 8-quinolinolate and a portion of the plasticizer andcompatibilizing agent may be prepared which may then be incorporatedinto the polymerized vinyl halide resin together with additionalquantities of plasticizer and compatibilizing agent.

After the homogeneous mixture of the plasticizer, N-alkylarylsulfonamide resin and copper 8-quinolinolate has been prepared, thismixture may be incorporated into the particular polymerized vinyl halideresin utilized according to any method commonly used and well known tothose skilled in the art. Thus, the homogeneous mixture of plasticizer,copper 8-quinolinolate and compatibilizing agent may be incorporatedwith the polyvinyl halide resin on a mixing or differential speed rollmill or in an internal mixer. This homogeneous mixture may also be addedto the latex of the resin, to an emulsion of the vinyl halide monomerprior to polymerization to form the resin, or to a solution of thepolymerized vinyl halide resin in a suitable solvent.

What is claimed is:

l. A process for preparing fungi and bacteria resistant vinylhalide-containing polymeric compositions which comprises incorporatinginto a vinyl halide-containing polymer in which more than 50% by weightis made from a vinyl halide a substantially homogeneous compositionobtained by heating a mixture comprising a plasticizer for said resin,an N-alkyl arylsulfonamide selected from the group consisting of N-alkylbenzenesulfonamides and N-alkyl toluenesulfonamides wherein the alkylsubstituent contains at least 1 and not more than 8 carbon atoms, and aminor but effective amount of copper 8-quinolinolate, the amount ofN-alkyl arylsulfonamide being sufiicient to compatibilize the copper 8-quinolinate in the resin composition.

2. A process for preparing fungi and bacteria resistant vinylhalide-containing polymeric compositions which comprises incorporatinginto a vinyl halide-containing polymer in which more than 50% by weightis made from a vinyl halide a substantially homogeneous compositionobtained by heating at a temperature in excess of about 100 C. a mixturecomprising a plasticizer for said resin, from about 1 to about 50 partsby weight of an N-alkyl arylsulfonamide selected from the groupconsisting of N-alkyl benzenesulfonamides and N-alkyltoluenesulfonamides wherein the alkyl substituent contains at least 1and not more than 8 carbon atoms per 100 parts of said resin, and fromabout 0.1 to about 10 parts by weight of copper 8-qu-inolinolate per 100parts of said resin.

3. A process for preparing fungi and bacteria resistant vinylhalide-containing polymeric compositions which comprises incorporatingintoa vinyl halide-containing polymer in which more than 50% by weightis made from a vinyl halide a substantially homogeneous compositionobtained by heating at a temperature in the range of from about 140 C.to about 200 C. a mixture comprising a plasticizer for said resin, fromabout 1 to about 10 parts by weight of an N-alkyl aryl-- sulfonamideselected from the group consisting of N-alkyl benzenesulfonamide andN-alliyl tol-- 0.1 to about 5 parts by weight of copper 8- quinolinolateper 100 parts of said resin.

4. A process for preparing fungi and bacteria resistant vinylchloride-containing polymeric compositions which comprises incorporatinginto a vinyl chloride-containing polymer in which more than 50% byweight is made from vinyl Q chloride a substantially homogeneouscomposition obtained by heating at a temperature in excess of about 100C. a mixture comprising a plasticizer for said resin, from about 1 toabout 10 parts by Weight of an N-alkyl arylsulfonami de selected thegroup consisting of N-alkyl benzenesulfonamide and N-alkyltoluenesulfonarnides wherein the alkyl substituent contains at least 1and not more than 8 carbon atoms per 100 parts of said resin, and fromabout 0.1 to about 5 partsby weight of copper 8-quinolinolate per 100parts of said resin.

5. A process for preparing fungi and bacteria resistant vinylchloride-containing polymeric: compositions which comprisesincorporating intoa vinyl chloride-containing polymer in which more than50% by weight is made from vinyl chloride a substantially homogeneouscomposition obtained by heating at a temperature in 12 the range of fromabout 140 C; to about 200 C". a mixture comprising a plasticizer forsaid resin, from about 1 to about 10 parts by weight of an N-alkylarylsulfonamide selected from the group consisting of N'-alkyl'benzenesulfonamide and N-alkyl toluenesulfonamides wherein the alkylsubstituent contains at least 1 and not more than 8 carbon atoms per 100parts of said resin, and from about 0.1 to about 5 parts by weight ofcopper 8-quinolinolate per 100 parts of said. resin.

6. A process as described in claim 5 wherein the vinylchloride-containing polymer is polyvinyl chloride.

'7. A process as described in claim 5 wherein the vinylchloride-containing polymer is a copolymer of vinyl chloride andunsaturated materials copolymerizable therewith.

8.. A process as. described in claim 5 wherein the vinylchloride-containing polymer is a. copolymer of vinyl chloride and vinylacetate- 9. A process as described in claim 5 wherein the vinylchloride-containing polymer is a. copolymer of vinyl chloride anddiethyl maleate in which at least about by weight. is made from vinylchloride.

10-. A process for preparing fungi and bacteria resistant vinylchloride-containing polymeric compositions which comprises incorporatinginto polyvinyl chloride a substantially homogeneous composition obtainedby heating at a temperature in the range of from about 140 C. to about200 C. a mixture comprising a plasticizer for polyvinyl chloride, fromabout 1 to about 10 parts by weight of N-ethyl toluenesulfonamide perparts of polyvinyl chloride, and from about 0.1 to about 5 parts byweight of copper 8- quinolinolate per 100 parts of polyvinyl chloride.

11. A process for preparing fungi and bacteria resistant vinylchloride-containing polymeric compositions which comprises incorporatinginto polyvinyl chloride a substantially homogeneous composition obtainedby heating at a. temperature in the range of from about C, to about 200C. a mixture comprising a plasticizer for polyvinyl chloride, from about1 to about 10 parts by weight of N-isopropyl benzenesulfonamide per 100parts of polyvinyl chloride, and from about 0.1 to about 5 parts byweight of copper 8- quinolinolate per 100 parts of polyvinyl chloride.

12. A process for preparing. fungi and bacteria. resistant vinylchloride-containing polymeric compositions which comprises incorporatingintopolyvinyl chloride a substantially homogeneous compositionobtainedby heating at a. temperature in the range of from about 140 C.to about. 200 C. a mixture comprising a plasticizer for. polyvinyl.

chloride, from about 1 to about 10 parts. by weightof N-isopropyltoluenesulfonamide per 100 parts of polyvinyl chloride, and from about0.1 to about 5 parts by weight of copper 8-quinolinolate per 100 partsof polyvinyl chloride.

References Cited in the file of this patent.

UNITED STATES PATENTS

1. A PROCESS FOR PREPARING FUNGI AND BACTERIA RESISTANT VINYLHALIDE-CONTAINING POLYMERIC COMPOSITIONS WHICH COMPRISES INCORPORATINGINTO A VINYL HALIDE-CONTAINING POLYMER IN WHICH MORE THAN 50% BY WEIGHTIS MADE FROM A VINYL HALIDE A SUBSTANTIALLY HOMOGENEOUS COMPOSITIONOBTAINED BY HEATING A MIXTURE COMPRISING A PLASTICIZER FOR SAID RESIN,AN N-ALKYL ARYLSULFONAMIDE SELECTED FORM THE GROUP CONSISTING OF N-ALKYLBENZENESULFONAMIDES AND N-ALKYL TOLUENESULFONAMIDES WHEREIN THE ALKYLSUBSTITUENT CONTAINS AT LEAST 1 AND NOT MORE THAN 8 CARBON ATOMS, AND AMINOR BUT EFFECTIVE AMOUNT OF COPPER 8-QUINOLINOLATE, THE AMOUNT OFN-ALKYL ARYLSULFONAMIDE BEING SUFFICIENT TO COMPATIBILIZE THE COPPER8QUINOLINATE IN THE RESIN COMPOSITION.